Protected aminofunctionalized polymerization initiators and methods of making and using same

ABSTRACT

Anionic polymerization initiators useful in the preparation of polymers having a protected amine functional group. The amine functionality includes a first protecting group, which can be aralkyl, methyl, allyl or tertiary alkyl group. The other of the amine protecting groups can be the same as the first protecting group. Alternatively, the second protecting group can be different from the first protecting group, in which case it is selected to have differential stability to agents used to remove the aralkyl, methyl, allyl or tertiary alkyl protecting group.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.09/655,528, filed Sep. 19, 2000 now U.S. Pat. No. 6,610,859, which is acontinuation-in-part of U.S. application Ser. No. 09/256,737, filed Feb.24, 1999 now U.S. Pat. No. 6,121,474, the disclosures of which areincorporated by reference herein in their entireties.

FIELD OF THE INVENTION

The present invention relates to polymerization initiators, and moreparticularly to anionic polymerization initiators having protected aminefunctionality, as well as processes for making and using the same andpolymers prepared using the initiators.

BACKGROUND OF THE INVENTION

Olefinic containing monomers can be polymerized using organo-alkalimetal initiators, such as butyllithium. The resultant intermediatepolymer contains an active alkali metal end group, which can besubsequently reacted with a suitable protonating, functionalizing, orcoupling or linking agent to replace the alkali metal with a more stableend group. In many applications, it can be useful to react the polymerliving end with a functionalizing agent, such as ethylene oxide, toprovide a polymer having a terminal functional group, such as ahydroxyl, carboxyl, or amine group.

Telechelic polymers contain two functional groups per molecule at thetermini of the polymer and are useful in a variety of applications. Forexample, telechelic polymers have been employed as rocket fuel binders,in coatings and sealants, and in adhesives. One approach that has beenused to prepare telechelic polymers is the generation and subsequentfunctionalization of a “dilithium initiator.” A dilithium initiator canbe prepared by the addition of two equivalents of secondary butyllithiumto meta-diisopropenylbenzene. The dilithium initiator is then reactedwith suitable monomers, such as butadiene, to form a polymer chain withtwo anionic sites. The resultant polymer chain is then reacted with twoequivalents of a functionalizing agent such as ethylene oxide.

While useful, gelation is frequently observed during thefunctionalization step. This leads to lower capping efficiencies (see,for example, U.S. Pat. No. 5,393,843, Example 1, wherein the cappingefficiency was only 82%). Additional details of this gelation phenomenaare described in U.S. Pat. No. 5,478,899. Further, this dilithiumapproach can only afford telechelic polymers with the same functionalgroup on each end of the polymer chain.

Progress has been made in the synthesis of dihydroxy terminatedpolymers. For example, monofunctional silyl ether initiators containingalkali metal end groups are disclosed in GB 2,241,239. Thesemonofunctional silyl ether initiators were demonstrated to be useful inproducing polybutadienes having an alpha protected hydroxyl functionalgroup. The living polymer can be reacted with suitable functionalizingagent such as ethylene oxide, and the silyl protecting group removed toprovide a dihydroxy telechelic polymer.

Monofunctional ether initiators of the formula M-Z-O—C(R¹R²R³) wherein Mis an alkali metal, Z is a branched or straight chain hydrocarbon tethergroup, and R¹, R² and R³ are independently defined as hydrogen, alkyl,substituted alkyl, aryl or substituted aryl, have also been proposed asanionic polymerization initiators to introduce a protected hydroxylfunctionality into a polymer. See U.S. Pat. No. 5,621,149. Thehydrocarbon solubility of such initiators can be increased by chainextension of the initiator with a conjugated diene. See U.S. Pat. No.5,565,526.

Anionic initiators containing a tertiary amine functionality have alsobeen proposed for use in hydrocarbon solvent polymerizations. Suchinitiators have the general formulaM-Z-N—(C—R¹R²R³)₂wherein M is defined as an alkali metal selected from lithium, sodiumand potassium; Z is defined as a branched or straight chain hydrocarbonconnecting group which contains 3-25 carbon atoms; and R¹, R² and R³ areindependently defined as hydrogen, alkyl, substituted alkyl groups, arylor substituted aryl groups. See M. J. Stewart, N. Shepherd, and D. M.Service, Brit. Polym. J., 22, 319-325 (1990).

However, these amine functional initiators possess low solubility inhydrocarbon solvents (typically less than 0.3 Molar in aliphatic orcycloaliphatic solvents like hexane or cyclohexane). The addition of anethereal co-solvent does increase the solubility of these initiators;however, this also increases the amount of 1,2-microstructure in theresultant polymer. See H. L. Hsieh and R. P. Quirk, AnionicPolymerization Principles and Practical Applications, pp. 397-400.Various other techniques have been employed to increase the solubilityof these initiators in hydrocarbon solvent. For example, chain extensionof the initiator with a conjugated diene increased the solubilityseveral fold. See U.S. Pat. No. 5,527,753.

The synthesis of diamino terminated polymers remains relativelyunexplored. Nakahama reports the preparation of amino terminatedpolystyrene by trapping the dianion with an electrophile that containeda protected amine group. A high degree of functionality was achieved bythis technique. See K. Ueda, A. Hirao, and S. Nakahama, Macromolecules,23, 939-945 (1990). However, the reaction conditions (−78° C., THFsolvent) were not practical for commercial production of thesefunctionalized polymers.

El-Aasser et al. recently reported the preparation of amino terminatedtelechelic polybutadiene by a free radical approach. See J. Xu, V. L.Dimonie, E. D. Sudol, and M. S. El-Aasser, Journal of Polymer Science:Part A: Polymer Chemistry, 33, 1353-1359 (1995). Since this is a freeradical synthesis, little control of molecular weight, molecular weightdistribution, and position of the amine functional group was obtained.

SUMMARY OF THE INVENTION

The present invention relates to protected amine functionalizedinitiators and processes for making and using the same to prepare aminefunctionalized polymers. The initiators of the invention include atertiary amine functionality. The amine functionality includes twoprotecting groups, which may be the same or different. When theprotecting groups are different, the groups are selected so as to havedifferential stability under specified deprotection conditions.Accordingly one of the protecting groups can be selectively removedwithout removing the other protecting group. In this manner, secondaryamine functionalized polymers can be readily prepared.

Specifically the initiators of the invention include compounds of theformula:

wherein:

M is an alkali metal selected from the group consisting of lithium,sodium and potassium;

Z is a branched or straight chain hydrocarbon connecting group whichcontains 3-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

Q is a saturated or unsaturated hydrocarbyl group derived by theincorporation of one or more unsaturated organic compounds, such as oneor more compounds selected from the group consisting of conjugated dienehydrocarbons, alkenylsubstituted aromatic compounds, and mixturesthereof, into the M-Z linkage;

n is from 0 to 5;

R¹ is a protecting group selected from the group consisting of aralkyl,allyl, tertiary alkyl, and methyl; and

R² can be the same as R¹, with the proviso that when R¹ is methyl, R² isnot C1-C4 alkyl, or R² can be different from R¹, in which case R² isselected from the group consisting of alkyl, substituted alkyl, alkoxy,substituted alkoxy, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, andsubstituted heterocycloalkyl, with the proviso that when R² is not thesame as R¹, then R² is more stable under conditions used to remove R¹,

or R¹ and R² together with the nitrogen atom to which they are attachedform

wherein y is from 1 to 4 and each R¹¹ is independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, cycloalkyl, substituted cycloalkyl, alkoxy,substituted alkoxy, heteroaryl, substituted heteroaryl,heterocycloalkyl, and substituted heterocycloalkyl.

In especially advantageous embodiments of the invention, the protectinggroup R¹ is aralkyl, preferably benzyl or a benzyl derivative; allyl; ortertiary alkyl, preferably tertiary butyl. In this aspect of theinvention, advantageously R² is the same as R¹. Alternatively, in thisaspect of the invention, R² is methyl. Examples of initiators of theinvention include without limitation3-[(N-benzyl-N-methyl)amino]-1-propyllithium,3-[(N,N-dibenzyl)amino]-1-propyllithium,3-[(N-tert-butyl-N-methyl)amino]-1-propyllithium,3-[(N,N-di-tert-butyl)amino]-1-propyllithium, and mixtures thereof.

These initiators can be treated with organometallic compounds,containing Mg, Zn, B, Al, and the like, to potentially afford highersolubility of the initiators in hydrocarbon solutions and/or livingpolymer stabilization. Other additives, such as those disclosed incopending U.S. Ser. No. 09/149,952, filed Sep. 9, 1998, and U.S. Ser.No. 09/512,494, filed Feb. 24, 2000, the entire disclosure of each ofwhich is hereby incorporated by reference, can also be used to improveinitiator solubility and/or living polymer stabilization.

The initiators are useful in polymerizing monomers capable of anionicpolymerization, including but not limited to conjugated dienes such asbutadiene and isoprene, alkenylsubstituted aromatic compounds such asstyrene, and mixtures thereof, to generate mono-, homo- orhetero-telechelic alpha amine functionalized polymers. The molecularweight of the polymers can vary widely, typically ranging from about 500up to 10,000,000, although the polymers can have a molecular weightoutside of this range as well. Advantageously the polymers have amolecular weight ranging from about 500 to about 20,000. The polymerscan also have a variety of microstructures. For some applications, thepolymers may have a 1,2 vinyl content ranging from about 20 to about80%. Again, however, the invention includes polymers having a 1,2 vinylcontent outside of this range, for example, from about 80% to about 100%1,2 vinyl content or less than about 20% 1,2 vinyl content to theminimum 1,2 vinyl content that can be achieved (currently about 4-5%).

The polymers of the invention initially have an alpha tertiary aminefunctionality. The protecting group R¹ is selected so that theprotecting group can be readily removed (or the amine functionality“deprotected”) under select conditions suitable for removing theprotecting group. For example, benzyl and benzyl derived protectinggroups can be removed under conditions used to hydrogenate unsaturationin the polymer chain. An allyl protecting group can be removed utilizinga rhodium catalyst. Methyl protecting groups can be removedphotochemically. Tertiary alkyl protecting groups can be removed by acidcatalyzed deprotection techniques.

As noted above, R² can be the same as R¹. In this aspect of theinvention, the resultant alpha tertiary amine functionalized polymerscan be treated to substantially simultaneously remove both R¹ and R² togive a polymer having an alpha primary amine functionality.

Alternatively, R¹ and R² are not the same. In this aspect of theinvention, R² is selected from suitable substituents which are morestable under the conditions used to remove R¹. As a result, R¹ can beremoved while R² remains intact to give an alpha secondary aminefunctionalized polymer. The alpha secondary amine functionalized polymercan be further treated to remove R², thus giving an alpha primary aminefunctionalized polymer.

The living polymers can be further treated to quench or functionalizethe living end thereof, for example, to provide near quantitative omegafunctionalized polymers (having for example hydroxyl, sulfide, carboxylor other functionality). The polymers also have substantiallyhomogeneous backbones, in contrast to polymers produced, for example,using dilithium initiator technology in which polymers include a crosslinked core.

The polymers can be hydrogenated to give a liquid, processablefunctionalized polymer. In one advantageous aspect of the invention, anunsaturated polymer of the invention having a protected alpha tertiaryamine functionality in which R¹ (and optionally R² as well) is benzyl ora benzyl derivative can be modified by replacing (or partiallyreplacing) the protecting group with a hydrogen atom using hydrogenationto concurrently saturate the polymer and remove the benzyl protectinggroup(s) to afford a saturated polymer with an alpha primary orsecondary amine functionality. The hydrogenation step can be performedfor polymers having reactive or non-reactive functionality at the omegaposition of the polymer chain.

Thus the present invention provides polymers containing an alphaprimary, secondary or tertiary amine functionality, optionally with areactive or non-reactive functionality at the omega position of thepolymer chain. Such polymers can be hydrogenated to afford a saturated(or partially saturated polymer) with an alpha primary, secondary ortertiary amine functionality. The protecting group can be present ordisplaced for the saturated or unsaturated polymers, depending upon thenature of the protecting group and the types of deprotection conditionsrequired to remove the same.

Examples of the types of polymers, without limitation that can beprepared in accordance with the present invention are illustrated below:

DETAILED DESCRIPTION OF THE INVENTION

The present invention now will be described more fully hereinafter withreference to the preferred embodiments of the invention. This inventionmay, however, be embodied in many different forms and should not beconstrued as limited to the embodiments set forth herein; rather, theseembodiments are provided so that this disclosure will be thorough andcomplete, and will fully convey the scope of the invention to thoseskilled in the art.

The present invention provides novel anionic initiators, which can behydrocarbon soluble, and mixtures of such initiators, containing atertiary amino group and having the following general structure:

wherein:

M is an alkali metal selected from the group consisting of lithium,sodium and potassium;

Z is a branched or straight chain hydrocarbon connecting group whichcontains 3-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

Q is a saturated or unsaturated hydrocarbyl group, and can be derived bythe incorporation of one or more unsaturated organic compounds, such asone or more compounds selected from the group consisting of conjugateddiene hydrocarbons, alkenylsubstituted aromatic compounds, and mixturesthereof, into the M-Z linkage;

n is from 0 to 5;

R¹ is a protecting group selected from the group consisting of aralkyl,preferably benzyl or benzyl derivative, allyl, tertiary alkyl,preferably tertiary butyl, and methyl; and

R² can be the same as R¹, with the proviso that when R¹ is methyl, R² isnot C1-C4 alkyl, or R² can be different from R¹, in which case R² isselected from the group consisting of alkyl, substituted alkyl, alkoxy,substituted alkoxy, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, andsubstituted heterocycloalkyl, with the proviso that when R² is not thesame as R¹, then R² is more stable under conditions used to remove R¹,

or R¹ and R² together with the nitrogen atom to which they are attachedform

wherein y is from 1 to 4 and each R¹¹ is independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, cycloalkyl, substituted cycloalkyl, alkoxy,substituted alkoxy, heteroaryl, substituted heteroaryl,heterocycloalkyl, and substituted heterocycloalkyl.

The term “aralkyl” generally refers to aralkyl groups in which the totalnumber of carbon atoms is no greater than about 18. The term aralkylincludes groups in which the alkylene chain and/or the aryl ring caninclude one or more heteroatoms, such as oxygen, nitrogen and sulfur.The alkylene chain and/or aryl ring can also be substituted with one ormore groups such as C1-C4 alkyl, C1-C4 alkoxy, and the like, so long asthe group does not interfere with the functionality of the benzylprotecting group and its removal, and/or with the activity of thelithium living end of the initiator.

Advantageous aralkyl groups in accordance with the invention are benzylgroups and benzyl derivatives. Benzyl derivatives include groups inwhich the phenyl ring is substituted with one or more groups such asC1-C4 alkyl, C1-C4 alkoxy, and the like, so long as the group does notinterfere with the functionality of the benzyl protecting group and itsremoval, and/or with the activity of the lithium living end of theinitiator. The term benzyl derivative also refers to benzyl groups inwhich the methylene linkage may also be substituted, for example, withone or more groups such as C1-C4 alkyl, C1-C4 alkoxy, aryl (phenyl) andthe like, again so long as the group does not interfere with thefunctionality of the benzyl protecting group and its removal, and/orwith the activity of the lithium living end of the initiator. Benzylderivatives also include groups in which the ring and/or methylene chaincan include heteroatoms, such as oxygen, sulfur or nitrogen. Suchsubstituted benzyl protecting groups can be represented by the generalformula:

in which n is from 1 to 5; and each R and R′ is independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, cycloalkyl, substituted cycloalkyl, alkoxy,substituted alkoxy, heteroaryl, substituted heteroaryl,heterocycloalkyl, substituted heterocycloalkyl, and the like, or atleast one R in combination with the phenyl ring forms a cyclic orbicyclic structure, such as

Exemplary R and R′ groups include without limitation methoxy, phenyl,methoxyphenyl, and the like. Exemplary substituted benzyl substituentsinclude without limitation 4-methoxybenzyl, 2,4-dimethoxybenzyl,diphenylmethyl, 4-methoxyphenylmethyl, triphenylmethyl,(4-methoxylphenyl)diphenylmethyl, and the like.

As used herein, the term “alkyl” refers to straight chain and branchedC1-C25 alkyl. The term “substituted alkyl” refers to C1-C25 alkylsubstituted with one or more lower C1-C10 alkyl, lower alkoxy, loweralkylthio, or lower dialkylamino. The term “cycloalkyl” refers to one ormore rings, typically of 5, 6 or 7 atoms, which rings may be fused orunfused, and generally including 3 to 12 carbon atoms. The term“substituted cycloalkyl” refers to cycloalkyl as defined above andsubstituted with one or more lower C1-C10 alkyl, lower alkoxy, loweralkylthio, or lower dialkylamino. The term “aryl” refers to C5-C25 arylhaving one or more aromatic rings, generally each of 5 or 6 carbonatoms. Multiple aryl rings may be fused, as in naphthyl or unfused, asin biphenyl. The term “substituted aryl” refers to C5-C25 arylsubstituted with one or more lower C1-C10 alkyl, lower alkoxy, loweralkylthio, or lower dialkylamino. Exemplary aryl and substituted arylgroups include, for example, phenyl, benzyl, and the like. The term“alkoxy” refers to straight chain and branched C1-C25 alkoxy. The term“substituted alkoxy” refers to C1-C25 alkoxy substituted with one ormore lower C1-C10 alkyl, lower alkoxy, lower alkylthio, or lowerdialkylamino. The terms “heteroaryl” and “substituted heteroaryl” referto aryl and substituted aryl as defined above which can include one tofour heteroatoms, like oxygen, sulfur, or nitrogen or a combinationthereof, which heteroaryl group is optionally substituted at carbonand/or nitrogen atom(s) with the groups such as noted above. The terms“heterocycloalkyl” and “substituted heterocycloalkyl” refer tocycloalkyl and substituted cycloalkyl as defined above having one ormore rings of 5, 6 or 7 atoms with or without saturation or aromaticcharacter and at least one ring atom which is not carbon. Exemplaryheteroatoms include sulfur, oxygen, and nitrogen. Multiple rings may befused or unfused.

The initiators of the invention are derived fromomega-tertiary-amino-1-haloalkanes and mixtures thereof of the followinggeneral structures:

wherein X is halogen, preferably chlorine or bromine; and Z, R¹ and R²are as defined above. In the process, selectedomega-tertiary-amino-1-haloalkanes, which alkyl groups contain 3 to 25carbon atoms, are reacted with an alkali metal typically at atemperature between about 35° C. and about 130° C., preferably at thereflux temperature of an alkane, cycloalkane, or aromatic reactionsolvent containing 5 to 12 carbon atoms and mixtures of such solvents.The resultant compound is a protected monofunctional organoalkali metalinitiator that is not chain extended having the formula

Tertiary amino-1-haloalkane raw materials (precursors) useful in thepractice of this invention are commercially available or can besynthesized using commercially available compounds. For example, theprecursor tertiary amino-1-haloalkanes can be prepared by the reactionof the corresponding amine with an alpha, omega dihalide, such as1-bromo-3-chloro-propane or 1,6-dichloro-hexane. This synthetic methodwas originally described by J. Almena, F. Foubelo, and M. Yus,Tetrahedron, 51, 11883-11890 (1995). In this regard, substantially 1:1molar ratios of the amine and dihaloalkane can be reacted in an inert ornon-polar solvent, such as cyclohexane, optionally in the presence of aphase transfer catalyst, followed by addition of NaOH.

A variation of this chemistry was recently disclosed in co-pendingapplication Ser. No. 08/882,513 (filed Jun. 25, 1997), the entiredisclosure of which is hereby incorporated by reference. See equationbelow:

In this procedure, an excess of the amine starting material was reactedwith an alpha, omega dihalide, such as 1-bromo-3-chloro-propane or1,6-dichloro-hexane. The excess amine served as an acid scavenger forthe acid liberated in the reaction. Each of these procedures affordedthe desired precursor molecules in high yield, and in high purity. Theprecursors could be purified, if desired, by conventional techniques,such as chromatography, distillation, or recrystallization. Typically,the precursors could be employed directly in the subsequent metallationreaction.

Compounds in which R¹ and R² together with the nitrogen atom to whichthey are attached form

wherein y and R¹¹ are as defined above can also be prepared using adihalo substrate

wherein each X is independently halo, and preferably each X is bromide.Such substrates are commercially available or can be prepared usingknown techniques. This dihalo substrate is reacted with thecorresponding amine generally represented by the formula NH₂-Z-X, inwhich X is also halo and preferably Cl, and Z is as defined above (forexample, —(CH₂)₃—), to prepare the halo amine precursor

Amines NH₂-Z-X are also commercially available or can be synthesizedusing known techniques.

Examples of tertiary amino-1-haloalkanes raw materials (precursors)useful in the practice of this invention include, but are not limitedto, 3-[(N-benzyl-N-methyl)amino]-1-propylhalide,3-[(N,N-dibenzyl)amino]-1-propylhalide,3-[(N-tert-butyl-N-methyl)amino]-1-propylhalide,3-[(N,N-di-tert-butyl)amino]-1-propylhalide,3-[(N-allyl-N-methyl)amino]-1-propylhalide,3-[(N,N-diallyl)amino]-1-propylhalide,2-methyl-3-[(N-benzyl-N-methyl)amino]-1-propylhalide,2-methyl-3-[(N,N-dibenzyl)amino]-1-propylhalide,2-methyl-3-[(N-tert-butyl-N-methyl)amino]-1-propylhalide,2-methyl-3-[(N,N-di-tert-butyl)amino]-1-propylhalide,2-methyl-3-[(N-allyl-N-methyl)amino]-1-propylhalide,2-methyl-3-[(N,N-diallyl)amino]-1-propylhalide,2,2-dimethyl-3-[(N-benzyl-N-methyl)amino]-1-propylhalide,2,2-dimethyl-3-[(N,N-dibenzyl)amino]-1-propylhalide,2,2-dimethyl-3-[(N-tert-butyl-N-methyl)amino]-1-propylhalide,2,2-dimethyl-3-[(N,N-di-tert-butyl)amino]-1-propylhalide,2,2-dimethyl-3-[(N-allyl-N-methyl)amino]-1-propylhalide,2,2-dimethyl-3-[(N,N-diallyl)amino]-1-propylhalide,4-[(N-benzyl-N-methyl)amino]-1-butylhalide,4-[(N,N-dibenzyl)amino]-1-butylhalide,4-[(N-tert-butyl-N-methyl)amino]-1-butylhalide,4-[(N,N-di-tert-butyl)amino]-1-butylhalide,4-[(N-allyl-N-methyl)amino]-1-butylhalide,4-[(N,N-diallyl)amino]-1-butylhalide,6-[(N-benzyl-N-methyl)amino]-1-hexylhalide,6-[(N,N-dibenzyl)amino]-1-hexylhalide,6-[(N-tert-butyl-N-methyl)amino]-1-hexylhalide,6-[(N,N-di-tert-butyl)amino]-1-hexylhalide,6-[(N-allyl-N-methyl)amino]-1-hexylhalide,6-[(N,N-diallyl)amino]-1-hexylhalide,8-[(N-benzyl-N-methyl)amino]-1-octylhalide,8-[(N,N-dibenzyl)amino]-1-octylhalide,8-[(N-tert-butyl-N-methyl)amino]-1-octylhalide,8-[(N,N-di-tert-butyl)amino]-1-octylhalide,8-[(N-allyl-N-methyl)amino]-1-octylhalide,8-[(N,N-diallyl)amino]-1-octylhalide, 3-[(N-methyl-N-C2-C25 alkyl orsubstituted alkyl)amino]-1-propylhalide, 2-methyl-3-[(N-methyl-N-C2-C25alkyl or substituted alkyl)amino]-1-propylhalide,2,2-dimethyl-3-[(N-methyl-N-C2-C25 alkyl or substitutedalkyl)amino]-1-propylhalide, 4-[(N-methyl-N-C2-C25 alkyl or substitutedalkyl)amino]-1-butylhalide, 6-[(N-methyl-N-C2-C25 alkyl or substitutedalkyl)amino]-1-hexylhalide, 8-[(N-methyl-N-C2-C25 alkyl or substitutedalkyl)amino]-1-octylhalide, 3-[(N-methyl-N-C5-C25 aryl or substitutedaryl)amino]-1-propylhalide, 2-methyl-3-[(N-methyl-N-C5-C25 aryl orsubstituted aryl)amino]-1-propylhalide,2,2-dimethyl-3-[(N-methyl-N-C5-C25 aryl or substitutedaryl)amino]-1-propylhalide, 4-[(N-methyl-N-C5-C25 aryl or substitutedaryl)amino]-1-butylhalide, 6-[(N-methyl-N-C5-C25 aryl or substitutedaryl)amino]-1-hexylhalide, 8-[(N-methyl-N-C5-C25 aryl or substitutedaryl)amino]-1-octylhalide, and the like and mixtures thereof. The halo-or halide group is selected from chlorine and bromine.

The alkali metal used in preparing the organometallic compoundscontaining tertiary amines, selected from lithium, sodium and potassium,is used as a dispersion whose particle size usually does not exceedabout 300 microns. Preferably the particle size is between 10 and 300microns although coarser particle size alkali metal can be used. Whenlithium metal is employed, the lithium metal can contain 0.2 to 5.0 andpreferably 0.8 weight percent sodium. The alkali metal is used inamounts of 90% of theoretical to a 400% excess above the theoreticalamount necessary to produce the compounds. The reaction temperature isgreater than about 35° C. up to just below the decomposition of thereactants and/or the product. An abrasive can be optionally added toimprove the metallation reaction. The yields of tertiary aminoorganometallic compounds prepared by this invention typically exceed85%.

The organoalkali metal initiators of the formulae

in which n is from greater than 0 to 5 are prepared by reacting acompound of the formulae

wherein M, Z, R¹, and R² have the meanings ascribed above, with one ormore unsaturated organic compounds, such as one or more conjugated dienehydrocarbons, one or more alkenylsubstituted aromatic compounds, ormixtures of one or more dienes with one or more alkenylsubstitutedaromatic compounds, to form an extended hydrocarbon chain between M andZ, which extended chain is denoted as Q_(n). The non-chain extendedinitiator is reacted with a one or more conjugated diene hydrocarbons,one or more alkenylsubstituted aromatic compounds, or mixtures of one ormore dienes with one or more alkenylsubstituted aromatic compounds,advantageously in a predominantly alkane, cycloalkane, or aromaticreaction solvent of 5 to 10 carbon atoms, and mixtures of such solvents,to produce a monofunctional initiator with an extended chain or tetherbetween the metal atom M and Z and mixtures thereof with the non-chainextended compounds. The chain extension reaction can be performed inseveral different manifolds.

In one embodiment, a dilute solution of the non-chain extended initiatorcan be separated from solid excess alkali metal and co-product alkalimetal halide (for example, the excess lithium metal and lithium chlorideby-product when a lithium metal dispersion is used). The chain extensionagent can then be added to the solution to increase the solubility ofthe non-chain extended initiator. Optionally, the concentration can beadjusted by removal of at least a portion of the solvent. In anotherembodiment, the chain extension agent is added to the reaction mixtureprior to filtration to remove the excess alkali metal and co-productalkali metal halide.

The chain extension can be carried out under a variety of conditions.Generally the chain extension reaction can be conducted at temperaturesranging from about −30° C. to about 150° C. The chain extension may alsobe conducted in the presence of certain Lewis bases, generally attemperatures sufficient to slow down polymerization, relative to chainextension. In this aspect of the invention, the Lewis base may be one ormore ethers, advantageously one or more aliphatic ethers, such as butnot limited to diethyl ether, dimethyl ether, methyl tertiary butylether (MTBE), tetrahydrofuran (THF), 2-methyltetrahydrofuran, and thelike and mixtures thereof. The Lewis base may also be one or moretertiary amines, such as aliphatic amines selected from the groupconsisting of trimethylamine, triethylamine, dimethylbutylamine,N,N,N′,N′-tetramethylethylenediamine (TMEDA), and the like as well asmixtures thereof. The proportion of these Lewis bases to theorganometallic being chain extended may be varied from about 0.05 moleto about 5.0 moles per mole of organometallic. The reaction temperatureused in the presence of the Lewis base may be lowered to about −30° C.to about +30° C. to prevent attack by the organometallic on the Lewisbase. As the skilled artisan will appreciate, however, the processconditions can depend on various factors such as the nature of Lewisbase, the nature of the organometallic, and the ratio of the Lewis baseto the organometallic, and can vary from the ranges given above.

In addition, as noted above, the chain extension reaction can be carriedout either prior to isolation of the organometallic species from thesolid excess alkali metal and co-product alkali metal halide, orsubsequent to the filtration. It is noted that not all of the initiatormust be chain extended, and the mixtures of chain extended and non-chainextended initiators can also provide benefits. It is also noted thatless than one equivalent chain extension (i.e., n is greater than 0 butless than 1) can still provide hydrocarbon solubility and iscontemplated to be within the scope of this invention.

The unsaturated organic chain extending compounds used in producing theinitiators of this invention are chosen from the group of organiccompounds that can be polymerized anionically in a reaction initiated byan alkali metal or its carbanionic derivative. Preferred are conjugateddienes and alkenyl substituted aromatic compounds, but other compoundscan also be used in accordance with the present invention so long as thecompound can form a chain extension.

Exemplary conjugated diene hydrocarbons include, but are not limited to,1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene(piperylene), myrcene, 2-methyl-3-ethyl-1,3-butadiene,2-methyl-3-ethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene,1,3-heptadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene,3-butyl-1,3-octadiene, 3,4-dimethyl-1,3-hexadiene,3-n-propyl-1,3-pentadiene, 4,5-diethyl-1,3-octadiene,2,4-diethyl-1,3-butadiene, 2,3-di-n-propyl-1,3-butadiene,2-methyl-3-isopropyl-1,3-butadiene, and the like and mixtures thereof.Other conjugated diene hydrocarbons can also be useful in practicingthis invention, such as those disclosed in U.S. Pat. No. 3,377,404.

The polymerizable alkenylsubstituted aromatic hydrocarbons useful inproducing the chain extended initiators of this invention include, butare not limited to, styrene, alpha-methylstyrene, vinyltoluene,2-vinylpyridine, 4-vinylpyridine, 1-vinylnaphthalene,2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene,2-alpha-methylvinylnaphathalene, 1,2-diphenyl-4-methyl-1-hexene, and thelike and mixtures of these, as well as alkyl, cycloalkyl, aryl, alkaryland aralkyl derivatives thereof in which the total number of carbonatoms in the combined hydrocarbon constituents is generally not greaterthan 18. Examples of these latter compounds include without limitation3-methylstyrene, 3,5-diethylstyrene, 2-ethyl-4-benzylstyrene,4-phenylstyrene, 4-p-tolylstyrene, 2,4-divinyltoluene,4,5-dimethyl-1-vinylnaphthalene, and the like and mixtures thereof.Reference is made to U.S. Pat. No. 3,377,404 for disclosure ofadditional alkenyl substituted aromatic compounds. Non-polymerizableconjugated dienes and alkenyl substituted aromatic compounds includingbut not limited to 1,1-diphenylethylene and 2,4-hexadiene may also beemployed as chain extension agents in accordance with the presentinvention.

The inert solvent employed during the preparation of the initiators ofthe present invention, or in subsequent polymerizations as discussed inmore detail below, for some applications is preferably a non-polarsolvent such as a hydrocarbon, since anionic polymerization in thepresence of such non-polar solvents is known to produce polyenes withhigh 1,4-contents from 1,3-dienes. Inert hydrocarbon solvents useful inpracticing this invention include but are not limited to inert liquidalkanes, cycloalkanes, aromatic solvents and mixtures thereof. Exemplaryalkanes and cycloalkanes can contain five to ten carbon atoms, such asbut not limited to pentane, hexane, cyclohexane, methylcyclohexane,heptane, methylcycloheptane, octane, decane and the like as well asmixtures thereof. Exemplary aromatic solvents can contain six to tencarbon atoms, such as but not limited to benzene, toluene, ethylbenzene,p-xylene, m-xylene, o-xylene, n-propylbenzene, isopropylbenzene,n-butylbenzene, and the like, and mixtures thereof.

While the compounds have been described herein as useful as anionicpolymerization initiators, it is noted that the compounds of theinvention as not so limited in use and can also be useful as reagents ina variety of synthesis applications.

The present invention also provides a process for the anionicpolymerization of anionically polymerizable monomers. The process of theinvention includes the step of initiating polymerization of one or moremonomers or compounds that can be anionically polymerized. Exemplaryanionically polymerizable compounds include conjugated diene hydrocarbonmonomers, a mixture of conjugated diene monomers, alkenyl substitutedaromatic compounds, a mixture of alkenyl substituted aromatic compounds,or a mixture of one or more conjugated diene hydrocarbons and one ormore alkenyl substituted aromatic compounds.

Other anionically polymerizable compounds can also be used as known inthe art, singly or in combination with one another or with other typesof monomer(s). For example, the monomers can include one or more polarmonomers such as, without limitation, esters, amides, and nitriles ofacrylic and methacrylic acid, and mixtures thereof with one anotherand/or with other monomers. Examples of polar monomers include withoutlimitation methyl methacrylate, methyl acrylate, t-butyl methacrylate,t-butyl acrylate, ethyl methacrylate, N,N-dimethylacrylamide, laurylmethacrylate, stearyl methacrylate, 2,3-epoxypropyl methacrylate, decylmethacrylate, and octyl methacrylate. For reference, see Macromolecules,14, 1599 (1981); Polymer 31, 106 (1990); Polymer, 34, 2875 (1993). Seealso U.S. Pat. No. 5,900,464.

The polymers of the invention can also include silicone block(s). Suchblocks can be prepared by anionically polymerizing one or more cyclicsiloxane monomers as known in the art. See U.S. Pat. No. 6,020,430.Generally such monomers can be defined by the formula (R¹R²SiO)_(y),wherein R¹ and R² are each independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, alkenyl, substitutedalkenyl, aryl, and substituted aryl and y=3-10.

Additional anionically polymerizable monomers include olefins such asethylene, porpylene, and the like. See U.S. Pat. No. 5,849,847.

The monomer(s) are polymerized in a hydrocarbon or mixedhydrocarbon-polar solvent medium generally at a temperature of 10° C. to150° C. with one or more initiators having the formula:

wherein R¹, R², Z, Q, n and M are as defined above. This provides anintermediate living polymer of the formula:

wherein:

P is a saturated or unsaturated hydrocarbyl group derived byincorporation of one or more anionically polymerizable compounds, suchas but not limited to, one or more compounds selected from the groupconsisting of conjugated diene hydrocarbons, alkenylsubstituted aromaticcompounds, and mixtures thereof;

m is from 2 to 20,000; and

M, Q, Z, R¹, R², and n have the meanings ascribed above.

The intermediate living polymer is then reacted with a suitableprotonating, functionalizing, or coupling or linking agent, as known inthe art.

In one aspect of the invention, the living polymer is reacted with afunctionalizing agent (or electrophile) of the formulaX—Y-T-(A-R⁴R⁵R⁶)_(k)wherein:

X is halide selected from the group consisting of chloride, bromide andiodide;

Y is a branched or straight chain hydrocarbon connecting group whichcontains 1-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

T is selected from the group consisting of oxygen, sulfur, and nitrogenand mixtures thereof;

A is an element selected from Group IVa of the Periodic Table of theElements;

R⁴, R⁵, and R⁶ are each independently selected from the group consistingof hydrogen, alkyl, substituted alkyl, aryl, substituted aryl,cycloalkyl, and substituted cycloalkyl, or R⁶ is optionally a—(CR⁷R⁸)_(l)— group linking two A when k is 2, wherein R⁷ and R⁸ areeach independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, andsubstituted cycloalkyl, and l is an integer from 1 to 7; and

k is 1 when T is oxygen or sulfur, and 2 when T is nitrogen. Thus theskilled artisan will appreciate that R⁶ as used herein includes thegroup

linking two A groups when k is 2.

The functionalizing agents can be prepared as described, for example, inInternational Publication WO 97/16465, the entire disclosure of which isincorporated by reference. In addition, the electrophiles can beprepared as described in K. Ueda, A. Hirao, and S. Nakahama,Macromolecules, 23, 939 (1990); U.S. Pat. No. 5,496,940; U.S. Pat. No.5,600,021; U.S. Pat. No. 5,362,699; A. Alexakis, M. Gardette, and S.Colin, Tetrahedron Letters, 29, 1988, 2951; B. Figadere, X. Franck, andA. Cave, Tetrahedron Letters, 34, 1993, 5893; J. Almena, F. Foubelo, andM. Yus, Tetrahedron, 51, 1995, 11883; D. F. Taber and Y. Wang, J. Org.Chem., 58, 1993, 6470; F. D. Toste and I. W. J. Still, Synlett, 1995,159; and U.S. Pat. No. 5,493,044. The functionalization step can beconducted at temperatures ranging from about −30° C. to about 150° C.

Other compounds useful in functionalizing living polymers include, butare not limited to, alkylene oxides, such as ethylene oxide, propyleneoxide, styrene oxide, and oxetane; oxygen; sulfur; carbon dioxide;halogens such as chlorine, bromine and iodine; propargyl halides;alkenylhalosilanes and omega-alkenylarylhalosilanes, such asstyrenyldimethyl chlorosilane; sulfonated compounds, such as 1,3-propanesultone; amides, including cyclic amides, such as caprolactam,N-benzylidene trimethylsilylamide, and dimethyl formamide; siliconacetals; 1,5-diazabicyclo[3.1.0]hexane; allyl halides, such as allylbromide and allyl chloride; methacryloyl chloride; amines, includingprimary, secondary, tertiary and cyclic amines, such as3-(dimethylamino)-propyl chloride andN-(benzylidene)trimethylsilylamine; haloalkyltrialkoxysilanes;epihalohydrins, such as epichlorohydrin, epibromohydrin, andepiiodohydrin, and other materials as known in the art to be useful forterminating or end capping polymers. These and other usefulfunctionalizing agents are described, for example, in U.S. Pat. Nos.3,786,116 and 4,409,357, the entire disclosure of each of which isincorporated herein by reference.

Other particularly advantageous functionalizing agents are imines.Imines are generally known in the art and can be described as having thegeneral formula:

wherein each R¹⁰ is independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl,substituted cycloalkyl, alkoxy, substituted alkoxy, heteroaryl;substituted heteroaryl, heterocycloalkyl, substituted heterocycloalkyl,and alkylsilyl (such as trimethylsilyl). Exemplary imine functionalizingagents include without limitation N-(benzylidene)trimethylsilylamine

(in which TMS is trimethylsilyl and Ph is phenyl); andN-(benzylidene)methylamine

Examples of difunctional coupling agents useful to form protectedtelechelic polymers include, but are not limited to, Me₂SiCl₂,Me₂Si(OMe)₂, Me₂SnCl₂, Ph₂SiCl₂, MePhSiCl₂, ClMe₂SiCH₂CH₂SiMe₂Cl, andMe₂SiBr₂, and the like and mixtures thereof.

Examples of useful multifunctional linking or coupling agents includeisomeric (mixtures of ortho, meta and para) dialkenylaryls and isomericdi- and trivinylaryls, such as 1,2-divinylbenzene, 1,3-divinylbenzene,1,4-divinylbenzene, 1,2,4-trivinylbenzenes, 1,3-divinylnaphthalenes,1,8-divinylnaphthalene, 1,2-diisopropenylbenzene,1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene,1,3,5-trivinylnaphthalene, and other suitable materials known in the artto be useful for coupling polymers, as well as mixtures of couplingagents. Other exemplary multifunctional linking or coupling agentsinclude halosilanes, halostannanes, phosphorus halides, and the like andmixtures thereof. Examples of the same include without limitation tintetrachloride (SnCl₄), silicon tetrachloride (SiCl₄), methyltrichlorosilane (MeSiCl₃), HSi(OMe)₃, Si(OEt)₄, Cl₃SiSiCl₃, phosphorustrichloride and the like and mixtures thereof. See also U.S. Pat. Nos.3,639,517 and 5,489,649, and R. P. Zelinski et al in J. Polym. Sci., A3,93, (1965) for these and additional coupling agents. Mixtures ofcoupling agents can also be used. Generally, the amount of couplingagent used is such that the molar ratio of protected living polymeranions to coupling agents ranges from 1:1 to 24:1. This linking processis described, for example, in U.S. Pat. No. 4,409,357 and by L. J.Fetters in Macromolecules, 9,732 (1976).

The resultant polymer thus can be a linear, homotelechelic,heterotelechelic, branched, or radial polymer having one or moreterminal tertiary amino functional groups. The polymer can be recoveredfrom the reaction media and optionally hydrogenated and/or deprotected.

If a mixture of monomers is employed in the polymerization, the monomerscan be added together to afford random or tapered block copolymers. Themonomers can also be charged to the reactor sequentially to afford blockcopolymers.

Monomer(s) to be anionically polymerized to form living polymer anionscan be selected from any suitable monomer capable of anionicpolymerization, including conjugated alkadienes, alkenylsubstitutedaromatic hydrocarbons, and mixtures thereof. Examples of suitableconjugated alkadienes include, but are not limited to, 1,3-butadiene,isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, myrcene,2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-pentadiene,1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene,3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene,3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-pentadiene,4,5-diethyl-1,3-octadiene, 2,4-diethyl-1,3-butadiene,2,3-di-n-propyl-1,3-butadiene, and 2-methyl-3-isopropyl-1,3-butadiene.

Examples of polymerizable alkenylsubstituted aromatic hydrocarbonsinclude, but are not limited to, styrene, alpha-methylstyrene,vinyltoluene, 2-vinylpyridine, 4-vinylpyridine, 1-vinylnaphthalene,2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene,2-alpha-methylvinylnaphthalene, 1,2-diphenyl-4-methyl-1-hexene andmixtures of these, as well as alkyl, cycloalkyl, aryl, alkylaryl andarylalkyl derivatives thereof in which the total number of carbon atomsin the combined hydrocarbon constituents is generally not greater than18. Examples of these latter compounds include 3-methylstyrene,3,5-diethylstyrene, 4-tert-butylstyrene, 2-ethyl-4-benzylstyrene,4-phenylstyrene, 4-p-tolylstyrene, 2,4-divinyltoluene and4,5-dimethyl-1-vinylnaphthalene. U.S. Pat. No. 3,377,404, incorporatedherein by reference in its entirety, discloses suitable additionalalkenylsubstituted aromatic compounds.

The inert solvent is preferably a non-polar solvent such as ahydrocarbon, since anionic polymerization in the presence of suchnon-polar solvents is known to produce polyenes with high 1,4-contentsfrom 1,3-dienes. Inert hydrocarbon solvents useful in practicing thisinvention include but are not limited to inert liquid alkanes,cycloalkanes and aromatic solvents and mixtures thereof. Exemplaryalkanes and cycloalkanes include those containing five to 10 carbonatoms, such as pentane, hexane, cyclohexane, methylcyclohexane, heptane,methylcycloheptane, octane, decane and the like and mixtures thereof.Exemplary aryl solvents include those containing six to ten carbonatoms, such as toluene, ethylbenzene, p-xylene, m-xylene, o-xylene,n-propylbenzene, isopropylbenzene, n-butylbenzene, and the like andmixtures thereof.

Polar solvents (modifiers), however, can be added to the polymerizationreaction to alter the microstructure of the resulting polymer, i.e.,increase the proportion of 1,2 (vinyl) microstructure or to promotefunctionalization or randomization. For certain applications, it can beadvantageous to provide polymers having from 20 to 80% 1,2 vinylmicrostructure. Examples of polar modifiers include, but are not limitedto: diethyl ether, dibutyl ether, tetrahydrofuran (THF),2-methyltetrahydrofuran, methyl tert-butyl ether (MTBE),diazabicyclo[2.2.2]octane (DABCO), triethylamine, tri-n-butylamine,N,N,N′,N′-tetramethylethylenediamine (TMEDA), and 1,2-dimethoxyethane(glyme). The amount of the polar modifier added depends on the vinylcontent desired, the nature of the monomer, the temperature of thepolymerization, and the identity of the polar modifier. The polarsolvent (modifier) can be added to the reaction medium at the beginningof the polymerization as part of the solvent reaction medium, addedduring the polymerization or after polymerization but prior tofunctionalization or coupling.

Unsaturation in the polymer chain may be treated as known in the art tomodify the same. For example, the unsaturated polymer may be reactedwith one or more epoxides to form one or more epoxy groups along thebackbone thereof.

The polymers produced may be optionally hydrogenated to affordadditional novel, functionalized polymers. Examples of methods tohydrogenate the polymers of this invention are described in Falk,Journal of Polymer Science: Part A-1, vol. 9, 2617-2623 (1971), Falk,Die Angewandte Chemie, 21, 17-23 (1972), U.S. Pat. Nos. 4,970,254,5,166,277, 5,393,843, 5,496,898, and 5,717,035. The hydrogenation of thefunctionalized polymer is conducted in situ, or in a suitable solvent,such as hexane, cyclohexane or heptane. This solution is contacted withhydrogen gas in the presence of a catalyst, such as a nickel catalyst.The hydrogenation is typically performed at temperatures from 25° C. to150° C., with an archetypal hydrogen pressure of 15 psig to 1000 psig.The progress of this hydrogenation can be monitored by InfraRed (IR)spectroscopy or Nuclear Magnetic Resonance (NMR) spectroscopy. Thehydrogenation reaction can be conducted until at least 90% of thealiphatic unsaturation has been saturated. The hydrogenated functionalpolymer is then recovered by conventional procedures, such as removal ofthe catalyst with aqueous acid wash, followed by solvent removal orprecipitation of the polymer.

The protecting group can be removed from the functionalized polymer, ifdesired. This deprotection can be conducted either prior to orsubsequent to the optional hydrogenation of the aliphatic unsaturation.Deprotection of these polymers affords a linear or radial polymer whichcontain either a mono-, di- or multi-functional terminal primary orsecondary amino group.

When the protecting group R¹ (and optionally R²) is aralkyl, andpreferably benzyl or benzyl derivative, then deprotection andhydrogenation can be performed concurrently. In this aspect of theinvention, the polymer can be partially hydrogenated under conditionsselected to leave the benzyl or benzyl derived protecting group intact.Alternatively the polymer can be partially hydrogenated so as to removethe benzyl or benzyl derived protecting group, yet substantiallyhydrogenate unsaturation in the polymer chain.

Various methods can be employed for the removal of the other tertiaryalkyl, such as tertiary butyl, allyl, or methyl protecting groups. Forexample, to remove tert-alkyl-protecting groups, the protected polymeris mixed with Amberlyst 15 ion exchange resin and heated at an elevatedtemperature, for example 150° C., until deprotection is complete. Inaddition, tert-alkyl-protecting groups can also be removed by reactionof the polymer with trifluoroacetic acid, or trimethylsilyliodide.Additional methods of deprotection of the tert-alkyl protecting groupscan be found in T. W. Greene and P. G. M. Wuts, Protective Groups inOrganic Synthesis, 3d Edition, Wiley, New York, 1999, page 574. See alsoU.S. Pat. No. 5,922,810, issued Jul. 13, 1999.

As noted above, aralkyl, such as benzyl and benzyl derived protectinggroups, can be removed under conditions used to hydrogenate polymers.See T. W. Greene and P. G. M. Wuts, Protective Groups in OrganicSynthesis, 3d Edition, Wiley, New York, 1999, pages 577-585 for this andother deprotection techniques for aralkyl protecting groups.Hydrogenation may also be used to remove the protecting group

as defined above to liberate the nitrogen atom. It is noted thathydrogenation conditions can be selected so as to partially hydrogenatethe polymer and leave the aralkyl, for example benzyl or benzylderivative, intact.

The allyl protecting group can be removed utilizing a rhodium catalyst.See B. C. Laguzza and B. Ganem, Tetrahedron Lett., 22, 1483 (1981).Reference is also made to T. W. Greene and P. G. M. Wuts, ProtectiveGroups in Organic Synthesis, 3d Edition, Wiley, New York, 1999, pages574-76.

Methyl protecting groups can be removed photochemically. For example,the methyl protecting groups can be cleaved or removed photochemicallyin the presence of an electron acceptor such as 9,10-dicyanoanthracene.J. Santamaria, R. Ouchabane, and J. Rigaudy, Tetrahedron Lett., 30, 2927(1989). Reference is also made to T. W. Greene and P. G. M. Wuts,Protective Groups in Organic Synthesis, 3d Edition, Wiley, New York,1999, pages 573-74.

After deprotection, the degree of functionality of the amino polymer canbe determined by the method of J. S. Fritz and G. H. Schenk,Quantitative Analytical Chemistry, 3rd edition; Allyn and Bacon, Inc.:Boston, 1974, p. 1974. The polymer was dissolved in a 1/1 mixture ofchloroform and glacial acetic acid, and titrated with perchloric acid,and with methyl violet as the indicator. The deprotection is generallynear quantitative to provide an amine functionality of about 1, or whena protected amine functionalized electrophile is used, about 2 forlinear polymers.

The resultant polymer can be a linear monofunctional polymer (resultingfrom quench of the living polymer with a protonating agent). The polymercan also be a linear telechelic polymer having two protected functionalgroups, in which the protecting group(s) and/or protectedfunctionalities can be the same or different. Polymers possessingsimilarly protected functional groups can be deprotected by selecting areagent specifically suited to remove the similar protecting groups.Alternatively, the invention also provides a process for the preparationof a linear polymer possessing one free telechelically functional groupand one protected telechelically functional group. In this aspect of theinvention, one type of protecting group is selectively deprotected froma dissimilarly protected functionality on the end(s) of the arms of thelinear polymer chains, produced as described above, using selectivereagents specifically suited to remove the targeted protective group andliberate the desired functionality, on the end of the polymer chain.

In yet another aspect of the invention, star or multi-branched polymersare produced by linking the living polymer anions using a coupling orlinking agent as known in the art (for example the multifunctionallinking agents as described above). The star polymers can be preparedusing the protected amine initiators of the present invention andmixtures of these initiators with one another as well as with otherprotected functionalized initiators having different protecting groupsand/or different protected functionalities. See, for example, U.S. Pat.Nos. 5,527,753, 5,827,929; 5,821,307; 5,919,870; 5,798,418; and5,780,551, for a discussion of various protected functionalizedinitiators and star or multi-branched polymers made using variousinitiators. In addition, other types of protected functionalizedinitiators and/or non-functional initiators as known in the art can alsobe used in combination with the initiators of the present invention. Theresultant polymers can have 3 to 30 arms. The protecting groups of thearms of the resultant star polymers can be removed, as discussed above,including the selective deprotection of dissimilar protecting groups.

The following table details experimental conditions that willselectively remove one of the protecting groups (more labile) from thepolymer, while retaining the other protecting group (more stable).

LABILE STABLE CONDITIONS t-Butyldimethylsilyl t Butyl Tetrabutylammoniumfluoride t-Butyldimethylsilyl t-Butyl 1 N HCl t-ButyldimethylsilylDialkylamino Tetrabutylammonium fluoride t-ButyldimethylsilylDialkylamino 1 N HCl t-Butyl Dialkylamino Amberlyst ® resin t-AmylDialkylamino Amberlyst ® resin Trimethylsilyl t-Butyl Tetrabutylammoniumfluoride Trimethylsilyl t-Butyl 1 N HCl Trimethylsilyl DialkylaminoTetrabutylammonium fluoride Trimethylsilyl Dialkylamino 1 N HC12,2,5,5-Tetramethyl-2,5- t-Butyl Tetrabutylammonium Fluoridedisila-1-azacyclopentane 2,2,5,5-Tetramethyl-2,5- t-Butyl 1 N HC1disila-1-azacyclopentane 2,2,5,5-Tetramethyl-2,5- DialkylaminoTetrabutylammonium Fluoride disila-1-azacyclopentane2,2,5,5-Tetramethyl-2,5- Dialkylamino 1 N HCl disila-1-azacyclopentane

In another aspect of this invention, unique polymers produced by theprocess described above are provided. The polymers produced by thisprocess may have linear, branched or radial architecture. Further, thepolymers may be monofunctional (produced by quench of the living anion),homotelechelic (for example, produced by coupling of the living anionwith a coupling agent with two active sites or by trapping of the livingpolymer anion with a protected, functionalized electrophileelectrophile), heterotelechelic (produced by quench of the livingpolymer anion with an electrophile), or polyfunctional (produced bycoupling of the living anion with a coupling agent with more than twoactive sites, such as tin tetrachloride or diisopropenylbenzene).

For example, exemplary monofunctional and telechelic polymers of theinvention are represented by the formulas below:

wherein:

Q, Z, R¹, R², and n have the meanings ascribed above;

P is a saturated or unsaturated hydrocarbyl group derived byincorporation of one or more anionically polymerizable compounds, suchas but not limited to compounds selected from the group consisting ofconjugated dienes, alkenylsubstituted aromatic hydrocarbons and mixturesthereof;

m is from 2 to 20,000; and

FG is hydrogen or a protected or unprotected functional group.Alternatively, FG can be a polymer segment derived by reaction of afunctional group with at least one comonomer.

The skilled artisan will appreciate that monofunctional polymers resultwhen FG is hydrogen, produced by quench of the living anion. Theresultant mono-functionalized polymer can be treated to remove one ofthe protecting groups (when R¹ and R² are not the same) or to removeboth protecting groups in one step (for example when R¹ and R² are thesame) or sequentially (when R¹ and R² are not the same and are removedunder different conditions). Removing one protecting group provides analpha secondary amine functionalized polymer of the formula

while removing both protecting groups (either simultaneously orsequentially) provides an alpha primary amine functionalized polymer ofthe formulaH₂N-Z-Qn-Pm-FGThe skilled artisan will appreciate that FG can also be a protected ornon-protected functional group or a polymer segment derived byincorporation of one or more comonomers with a functional group.

Telechelic polymers (both homotelechelic and heterotelechelic) can beprepared by reaction of the living polymer with any of the types offunctionalizing agents or electrophiles as known in the art described inmore detail above. For example, homotelechelic polymers can be producedby trapping of the living polymer anion with a protected, functionalizedelectrophile. Heterotelechelic polymers include those polymers in whichFG and the omega protected amine functionality are different. In oneaspect of the invention, heterotelechelic polymers include polymerswhich have been terminated using a functionalizing agent (orelectrophile) of the formula X—Y-T-(A-R⁴R⁵R⁶)k wherein X, Y, T, A, R⁴,R⁵, R⁶ and k are the same as defined above. Exemplary polymersfunctionalized with such an electrophile can have the structure below:

wherein Y, Z, T, A, P, Q, k, m, n, R¹, R², R⁴, R⁵, and R⁶ are the sameascribed above (i.e., FG is —Y-T-(A(R⁴R⁵R⁶)k). In one advantageousembodiment of the invention the polymer has the formula:

wherein Y, Z, P, Q, m, n, R¹, and R² are the same ascribed above.

The protected linear functionalized polymers can be treated to removeone, two or more protecting groups as described above. The resultantdeprotected functionalized polymers can have the following structures:

(removal of R¹ alone), H₂N-Z-Qn-Pm—Y-T(AR⁴R⁵R⁶)k(simultaneous or sequential removal of R¹ and R²),H₂N-Z-Qn-Pm—Y-T(H)k(simultaneous or sequential removal of R¹, R² and -AR⁴R⁵R⁶),

(removal of -AR⁴R⁵R⁶), and

(removal of R¹ and -AR⁴R⁵R⁶).

In a particularly advantageous embodiment of the invention, the polymerincludes two R¹ protecting groups which are the same and both R¹s areremoved to provide an alpha, omega secondary diamine functionalizedpolymer of the formula

In another aspect of the invention, heterotelechelic polymers includepolymers which have been terminated using an imine functionalizing agent(or electrophile) of the formula

wherein each R¹⁰ is as defined above. The resultant polymerfunctionalized with an imine electrophile can have the structure below:

wherein R¹, R², Z, Q, n, P, m, and R¹⁰ have the meanings as set forthabove. One, two or more protecting groups can be removed in this aspectof the invention as well.

One exemplary polymer of this aspect of the invention has the formula

wherein Ph is phenyl and Me is methyl. In this aspect of the invention,when R¹ is methyl, the polymer can be treated remove both methyl groupsto provide a diamine functionalized polymer having a secondary aminefunctionality and a primary amine functionality, i.e.,

When R¹ is not methyl, the polymers can be treated to selectively removeeither the R¹ protecting group or the methyl group to provide polymersof the formula:

(remove R¹ and R², either simultaneously or sequentially).

Complete deprotection or removal of the protecting groups providespolymers of the formula

Another exemplary polymer in this aspect of the invention can have thestructure:

wherein TMS is trimethylsilyl. Again the various groups on the aminefunctionalities can be removed to provide polymers such as

(remove both R¹ and R², either simultaneously or sequentially).

Also in this embodiment of the invention, it is noted that the livingpolymer can be reacted with an imine and rather than isolating theresultant imine functionalized polymer as described above, anintermediate polymer of the formula

can be directed to an additional step in which the nitrogen atom isreacted with a suitable agent to form a polymer having to polymersegment or functionality as represented generally below:

in which X is a polymer segment or functionality derived by reaction ofa suitable reagent with the imine intermediate and R¹⁰ attached to the Natom may be present or absent depending upon the reaction. For example,the intermediate polymer can be reacted with diisocyanate to form apolymer having at least one isocyanate group as illustrated below:

Particularly preferred polymers include polymers having telechelicprimary and/or secondary amine groups, as well as their hydrogenatedanalogs. A primary amine results when all protecting groups are removedfrom a protected amine functionality. A secondary amine results when onebut not another protecting group is removed from a protected aminefunctionality. The primary and secondary amine groups can be representedgenerally by the formula —N(H)R, in which R is hydrogen (primary amine)or R² as defined above (secondary amine).

The newly liberated primary or secondary amino groups can thenparticipate in subsequent polymerization chemistry. For example, a monoprimary or secondary amine and/or a telechelic primary or secondarydiamine can react with a diisocyanate to afford a polyurethane.Advantageously the diisocyanate is a non-symmetrical diisocyanate, suchas isophorone diisocyanate, as shown below:

Preferably an excess amount of diisocyanate is used to minimize orprevent chain extension. After the diisocynate is reacted with the amineterminated polymer, the isocyanate groups on the terminal ends of thepolymer may be blocked. This allows the polymers to be used informulations with diols and other groups which normally react withisocyanates, such as coating systems either in solvents or aqueoussystems. See U.S. Pat. No. 5,710,209.

The newly liberated primary or secondary amino groups can also reactwith an unreacted epoxy group (oxirane) groups to form partially orfully crosslinked epoxy resins. Similar to the diisocyanates,advantageously an unsymmetrical diepoxide reagent is used in excessamounts to minimize or prevent chain extension. An exemplaryunsymmetrical diepoxide is

However, any diepoxide can be used, such as the diglycidyl ether ofBisphenol A (DGEBA). Other aromatic epoxies can be used such as thediglycidyl ether of Bisphenol F, or the diglycidyl ether of resorcinol.For improved thermal oxidative and UV stability, cycloaliphatic epoxiescan be used.

In another aspect of the invention, one or more primary and/or secondaryamines can be reacted with excess anhydride, such as maleic anhydride

to form a polymer having one or more terminal carboxyl functionalities—COOH.

In yet another aspect of the invention, one or more primary or/andsecondary amines can be reacted with glycidyl methacrylate

to form a polymer having one or more terminal olefinic groups —C(R)═CH₂,wherein R can be methyl).

In yet another aspect of the invention, one or more primary or/andsecondary amines can be reacted with glycidol

to provide a hydroxyl terminated polymer with an epoxy group.

Condensation polymers can also be prepared. For example, a polyamidecondensation polymer can be synthesized from a telechelic diamine and adicarboxylic acid.

The skilled artisan will appreciate that these and other reactions canbe conducted on one or more terminal ends of the polymers of theinvention.

In addition, when the living chain end is reacted with a protectedfunctionalized electrophile, the resultant protected functionality canalso be deprotected, and the liberated functionality can optionally bereacted with one or more comonomers to polymerize a functional endthereof. Exemplary comonomers include without limitation cyclic ethers,diamines, diisocyanates, polyisocyanates, di-, poly- and cyclic amides,di- and polycarboxylic acids, diols, polyols, anhydrides, and the likeand mixtures thereof. For example, functionalized polymers can befurther reacted with monofunctional monomers, such as caprolactam, orother lactams, to form a polyamide block polymer segment, or cyclicethers such ethylene oxide to form polyether blocks; or withdifunctional monomers, such as diacids or anhydrides and diamines toform polyamide blocks, or diacids or anhydrides or lactones and diols toform polyester blocks, or diols and polyols with diisocyanates orpolyisocyanates to form polyurethane blocks. Polyisocyanates orpolyfunctional polyols are examples of polyfunctional monomers. Thefunctional group may also be reacted with a suitable agent containing areactive olefinic bond, such as a styrenic or acrylic functionality,such as methacroyl chloride, which will act to change the nature of thefunctionality and provide a “macromonomer” capable of polymerizing withother free radically polymerizable monomers.

In yet another aspect of the invention, two or more living polymers canbe linked using a coupling or linking agent as known in the art. In oneembodiment of this aspect of the invention, the linking agent is adifunctional linking agent. The resultant homotelechelic polymer isrepresented by the below formula:L-[Pm-Qn-Z-N(R¹)(R²)]₂wherein:

each R¹, R², P, Q, Z, m and n independently have the meanings ascribedabove; and

L is a residue of a difunctional linking agent, such as SiMe₂ residuederived form the difunctional linking agent SiMe₂Cl₂.

In another embodiment of this aspect of the invention, the linking agentis a multifunctional linking agent. The resultant star or multi-branchedpolymer is represented by the below formula:L′-[Pm-Qn-Z-N(R¹)(R²)]_(v)wherein:

each R¹, R², P, Q, Z, m and n independently have the meanings ascribedabove;

L′ is a residue of a multifunctional linking agent, such asdivinylbenzene; and

v is from 3 to 30. As the skilled artisan will appreciate, each R¹, R²,P, Q, Z, m and n can differ if the coupled living polymers are preparedusing different protected functionalized and/or non-functionalinitiators. Such polymers prepared using different protectedfunctionalized initiators and/or non-functional initiators can bepresented as follows:L′-[Pm-Qn-Z-N(R¹)(R²)]_(30-v)[Pm—B]_(v)wherein:

R¹, R², P, Q, Z, m, n, L′, and v have the meanings ascribed above; and

each [Pm—B] can be the same or different and each P and m is as definedabove and each B is independently selected from the residue of analkyllithium initiator (i.e., a non-functional initiator) or a protectedfunctionalized initiator, in which the protecting group is intact orremoved. The skilled artisan will appreciate that each arm can be thesame length or different lengths and can include the same or differentmonomer composition.

As discussed above, these homotelechelic and star or multi-branchedpolymers can be hydrogenated, deprotected and/or further reacted withone or more comonomers to form polymer segments. Particularly preferredpolymers include homotelechelic and star or multibranched polymershaving primary and/or secondary amine groups, as well as theirhydrogenated analogs. As noted above, primary amines result from theremoval of both protecting groups R¹ and R² and secondary amines resultfrom the removal of protecting group R¹. The primary and secondary aminegroups are represented generally by the formula —N(H)R, in which R ishydrogen (primary amine) or R² as defined above.

The molecular architecture of compounds of the present invention can beprecisely controlled. The degree of functionality can be adjusted bysimply varying the ratio of tertiary amino functional initiator tocoupling agent. Further, the monomer identity, the monomer compositionand molecular weight can be independently manipulated by varying themonomer charged. Finally, the number of polymer arms can be adjusted byvarying the nature of the coupling agent, and the ratio of livingpolymer to the coupling agent.

Non-hydrogenated linear or radial polymers prepared with the amineinitiators of the present invention, including homopolymers of dienes,block or random copolymers of different dienes, or block or randomcopolymers of dienes and alkenylsubstituted aromatic monomers,possessing tertiary amine functional groups, are useful for productionof elastomeric compounds exhibiting reduced hysteresis characteristics.Introduction of functional groups, particularly amino functional groupsto the termini of polymer chains of polymers used in tire compounds inparticular, has resulted in lowered hysteresis properties which areassociated with reduced rolling resistance and heat build-up duringoperation of the tire. Examples of the use of amine functional polymersfor such applications are described in U.S. Pat. Nos. 5,959,048,5,935,893, 5,932,662, 5,916,961, 5,912,343, 5,902,856, 5,880,206,5,502,131, 5,496,940, 5,491,230, 5,332,810, 5,274,106, 5,238,893,5,219,942, 5,216,080, 5,115,006, 4,614,771, the disclosures of which areincorporated herein by reference.

The present invention will be further illustrated by the followingnon-limiting examples.

Preparation of Initiators EXAMPLE 1 Preparation of Initiator Precursor3-[(N-benzyl-N-methyl)amino]-1-propylchloride

To a stirred suspension of K₂CO₃ (200 g, 1.5 mole) in cyclohexane 200 mLand 1-bromo-3-chloropropane (“BCP”) (540 g, 3.4 mole) was added dropwiseover a period of 1 hour at 20° C. benzylmethyl amine (272 g, 2.24 mole).After complete addition the reaction was allowed to stir for anadditional 20 hours. The crude reaction mixture was filtered and thenwashed with saturated NaCl (3×100 mL). The organic phase was extractedwith 3N HCl (3×100 mL). The resulting aqueous phase, containing thedesired product as the hydrochloric salt, was washed with hexanes (3×100mL) to remove any residual BCP. The aqueous phase was subsequentlybasified with 50 wt % NaOH and extracted with cyclohexane (3×100 mL).After solvent removal 220 g (50% yield) of the title compound wasisolated as a yellow oil.

EXAMPLE 2 Preparation of 3-[(N-benzyl-N-methyl)amino]-1-propyllithium

To a 500 ml Morton/cleave flask reactor under argon atmosphere was addedlithium powder (13.32 g, 1.92 mole) and 141 grams of cyclohexane. To aconstant addition funnel was added3-[(N-benzyl-N-methyl)amino]-1-propylchloride (70.93 g, 0.34 mol) and83.3 grams cyclohexane. Immediately before beginning the addition, thelithium metal mixture was heated to 53° C. using a heating mantel.Dropwise addition of the feed solution was performed while maintainingthe reaction temperature at 50° C. A cooling bath of hexane, to whichdry ice was added periodically, was employed to maintain a reactiontemperature between 48° to 51° C. The total addition time was 1.22 hourswith an average stirring rpm of 925. The reaction mixture was stirred atleast one hour after the feed was completed. This mixture was thenpumped through a ⅜″ teflon tube to a pressure filter that containedabout 10 grams of filter aid and filtered under an argon atmosphere. Thereactor was then rinsed 3×50 ml cyclohexane, each time transferred tothe muds that were also washed with the rinse. The final product was 420g of light amber solution. Analysis by WE titration indicated a 99%yield of active base (0.809 mole/kg). GC-MS (TMS derivative): Calculatedfragment masses: 235, 220, 134, 91, 73; Observed fragment masses: 235,220, 134, 91, 73.

EXAMPLE 3 Preparation of Initiator Precursor3-[(N,N-dibenzylamino]-1-propylchloride

To a stirred suspension of K₂CO₃ (200 g, 1.5 mole) in cyclohexane 200 mLand 1-bromo-3-chloropropane (540 gms, 3.4 mole) is added dropwise over aperiod of 1 h at 20° C. dibenzyl amine (442 g, 2.24 mole). Aftercomplete addition the reaction is allowed to stir for an additional 20h. The crude reaction mixture is filtered and then washed with saturatedNaCl (3×100 mL). The organic phase is extracted with 3N HCl (3×100 mL).The resulting aqueous phase, containing the desired product as thehydrochloric salt, is washed with hexanes (3×100 mL) to remove anyresidual BCP. The aqueous phase is subsequently basified with 50 wt %NaOH and extracted with cyclohexane (3×100 mL). After solvent removal324 g (53% yield) of the title compound was isolated as a yellow oil.

EXAMPLE 4 Preparation of 3-[(N,N-dibenzylamino]-1-propyllithium

To a 500 ml Morton/cleave flask reactor under argon atmosphere is addedlithium powder (13.32 g, 1.92 mole) and 141 grams of cyclohexane. To aconstant addition funnel is added3-[(N,N-dibenzylamino]-1-propylchloride (92.8 g, 0.34 mol) and 83.3grams cyclohexane. Immediately before beginning the addition, thelithium metal mixture is heated to 53° C. using a heating mantel.Dropwise addition of the feed solution is performed while maintainingthe reaction temperature at 50° C. A cooling bath of hexane, to whichdry ice is added periodically, is employed to maintain a reactiontemperature between 48° to 51° C. The total addition time is 1.22 hourswith an average stirring rpm of 925. The reaction mixture is stirred atleast one hour after the feed was completed. This mixture is then pumpedthrough a ⅜″ teflon tube to a pressure filter that contains about 10grams of filter aid and is filtered under an argon atmosphere. Thereactor is then rinsed 3×50 ml cyclohexane, each time transferred to themuds that were also washed with the rinse. The final product is 420 g oflight amber solution. Analysis by WE titration indicates a 99% yield ofactive base (0.809 mole/kg).

EXAMPLE 5 Preparation of Initiator Precursor3-[(N-t-Butyl-N-methyl)amino]-1-propylchloride

To a stirred suspension of K₂CO₃ (200 g, 1.5 mole) in cyclohexane 200 mLand 1-bromo-3-chloropropane (540 gms, 3.4 mole) is added dropwise over aperiod of 1 h at 20° C. t-butylmethyl amine (194 g, 2.24 mole). Aftercomplete addition the reaction is allowed to stir for an additional 20h. The crude reaction mixture is filtered and then washed with saturatedNaCl (3×100 mL). The organic phase is extracted with 3N HCl (3×100 mL).The resulting aqueous phase, containing the desired product as thehydrochloric salt, is washed with hexanes (3×100 mL) to remove anyresidual BCP. The aqueous phase is subsequently basified with 50 wt %NaOH and extracted with cyclohexane (3×100 mL). After solvent removal186 g (51% yield) of the title compound is isolated as a yellow oil.

EXAMPLE 6 Preparation of 3-[(N-t-Butyl-N-methyl)amino]-1-propyllithium

To a 500 ml Morton/cleave flask reactor under argon atmosphere is addedlithium powder (13.32 g, 1.92 mole) and 141 grams of cyclohexane. To aconstant addition funnel was added3-[(N-t-Butyl-N-methyl)amino]-1-propylchoride (55.6 g, 0.34 mol) and83.3 grams cyclohexane. Immediately before beginning the addition, thelithium metal mixture is heated to 53° C. using a heating mantel.Dropwise addition of the feed solution is performed while maintainingthe reaction temperature at 50° C. A cooling bath of hexane, to whichdry ice is added periodically, is employed to maintain a reactiontemperature between 480 to 51° C. The total addition time is 1.22 hourswith an average stirring rpm of 925. The reaction mixture is stirred atleast one hour after the feed is completed. This mixture is then pumpedthrough a ⅜″ teflon tube to a pressure filter that contains about 10grams of filter aid and filtered under an argon atmosphere. The reactoris then rinsed 3×50 ml cyclohexane, each time transferred to the mudsthat are also washed with the rinse. The final product is 420 g of lightamber solution. Analysis by WE titration indicated a 99% yield of activebase (0.809 mole/kg).

EXAMPLE 7 Preparation of Initiator Precursor3-[(N,N-di-t-Butyl)amino]-1-propylchloride

To a stirred suspension of K₂CO₃ (200 g, 1.5 mole) in cyclohexane 200 mLand 1-bromo-3-chloropropane (540 gms, 3.4 mole) is added dropwise over aperiod of 1 h at 20C di-t-butyl amine (289 g, 2.24 mole). After completeaddition the reaction is allowed to stir for an additional 20 h. Thecrude reaction mixture is filtered and then washed with saturated NaCl(3×100 mL). The organic phase is extracted with 3N HCl (3×100 mL). Theresulting aqueous phase, containing the desired product as thehydrochloric salt, is washed with hexanes (3×100 mL) to remove anyresidual BCP. The aqueous phase is subsequently basified with 50 wt %NaOH and extracted with cyclohexane (3×100 mL). After solvent removal234 g (51% yield) of the title compound is isolated as a yellow oil.

EXAMPLE 8 Preparation of 3-[(N,N-di-t-Butyl)amino]-1-propyllithium

To a 500 ml Morton/cleave flask reactor under argon atmosphere is addedlithium powder (13.32 g, 1.92 mole) and 141 grams of cyclohexane. To aconstant addition funnel is added3-[(N,N-di-t-butyl)amino]-1-propylchoride (69.7 g, 0.34 mol) and 83.3grams cyclohexane. Immediately before beginning the addition, thelithium metal mixture is heated to 53° C. using a heating mantel.Dropwise addition of the feed solution is performed while maintainingthe reaction temperature at 50° C. A cooling bath of hexane, to whichdry ice is added periodically, is employed to maintain a reactiontemperature between 48° to 51° C. The total addition time is 1.22 hourswith an average stirring rpm of 925. The reaction mixture is stirred atleast one hour after the feed is completed. This mixture is then pumpedthrough a ⅜″ teflon tube to a pressure filter that contains about 10grams of filter aid and filtered under an argon atmosphere. The reactoris then rinsed 3×50 ml cyclohexane, each time transferred to the mudsthat were also washed with the rinse. The final product is 428.90 g oflight amber solution. Analysis by WE titration indicated a 99% yield ofactive base (0.809 mole/kg).

Preparation of Polymers EXAMPLE 9 Preparation of Protected-Alpha-3°Amine Functionalized Polyisoprene

A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N-benzyl-N-methyl)amino]-1-propyllithium 0.82 mmoles (0.14 gramsactive of 14.0 wt % in cyclohexane), and purified cyclohexane (195 g).The reactor is then flame sealed off. Diethylether 23 grams (0.31 mole)was added from a break-seal ampoule. Purified isoprene monomer (10.20grams, 150 mmoles) is added from a break-seal ampoule. The reactionmixture is stirred for twenty four hours at room temperature. Theliving, functionalized poly(isoprenyl)lithium is terminated withdegassed methanol from the last ampoule.2,6-Di-tert-butyl-4-methylphenol (BHT, 0.01%) is added to the polymersolution as an antioxidant. The resultant protected, functionalizedpolymer is isolated by concentration of the organic solution. Theresultant functionalized polyisoprene polymer is characterized by SEC(polyisoprene standards), and had the following properties: M_(n)=5,200g/mole, M_(w)=5,300 g/mole, M_(w)/M_(n)=1.03. ¹H NMR verifies amicrostructure of 55% 1,4 enchainment, and the presence of the benzylprotecting group on the amine functionality.

EXAMPLE 10 Preparation of Alpha-2° Amine Functionalized Polyisoprene

A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N-benzyl-N-methyl)amino]-1-propyllithium 0.82 mmoles (0.14 gramsactive of 14.0 wt % in cyclohexane), and purified cyclohexane (195 g).The reactor is then flame sealed off. Diethylether 23 grams (0.31 mole)was added from a break-seal ampoule. Purified isoprene monomer (10.20grams, 150 mmoles) is added from a break-seal ampoule. The reactionmixture is stirred for twenty four hours at room temperature. Theresulting reaction mixture is transferred to a 500 mL autoclave andsparged with hydrogen at 45° C. The reactor is pressurized to 700 psigwith hydrogen and a Ni/Al catalyst is added slowly to control theresulting exothermic reaction. Enough catalyst is added to achieve asolution concentration of nickel to 100 ppm. (The catalyst is preparedin advance by reacting 1 molar eq. of nickel(II) 2-ethylhexanote with 2molar eq. of triethylaluminum in cyclohexane). After 2 hr ofhydrogenation, the reaction is allowed to cool to room temperature,depressurized and purged with nitrogen. The resultant functionalizedpolymer is precipitated into a large amount of methanol, filtered andwashed with additional methanol. The resultant hydrogenatedfunctionalized polyisoprene polymer is characterized by ¹H NMR whichverifies near quantitative hydrogenation (>97%) of the unsaturation inthe backbone and deprotection (>97%) of the benzyl protecting group fromthe amine functionality to afford an alpha secondary amine.

EXAMPLE 11 Preparation of Alpha, Omega-2° Amine FunctionalizedPolyisoprene

A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N-benzyl-N-methyl)amino]-1-propyllithium 0.82 mmoles (0.14 gramsactive of 14.0 wt % in cyclohexane), and purified cyclohexane (195 g).The reactor is then flame sealed off. Diethylether 23 grams (0.31 mole)is added from a break-seal ampoule. Purified isoprene monomer (10.20grams, 150 mmoles) is added from a break-seal ampoule. The reactionmixture is stirred for twenty four hours at room temperature. To theliving polymer is added 3-[(N-benzyl-N-methyl)amino]-1-propylchoride(0.16 g, 0.9 mmoles) and is stirred for an additional 15 h at roomtemperature. The resulting reaction mixture is transferred to a 500 mLautoclave and sparged with hydrogen at 45° C. The reactor is pressurizedto 700 psig with hydrogen and a Ni/Al catalyst is added slowly tocontrol the resulting exothermic reaction. Enough catalyst is added toachieve a solution concentration of nickel to 100 ppm. (The catalyst isprepared in advance by reacting 1 molar eq. of nickel(II)2-ethylhexanote with 2 molar eq. of triethylaluminum in cyclohekane).After 2 hr of hydrogenation, the reaction is allowed to cool to roomtemperature, depressurized and purged with nitrogen. The resultanthydrogenated functionalized polyisoprene polymer is characterized by ¹HNMR which verifies near quantitative hydrogenation (>97%) of theunsaturation in the backbone and deprotection (>97%) of the benzylprotecting groups from the amine functionality to afford saturatedpolyisoprene with alpha, omega secondary amine functionalities.

EXAMPLE 12 Preparation of Protected-Alpha-3° AmineFunctionalized-Polybutadiene

A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N-benzyl-N-methyl)amino]-1-propyllithium 0.82 mmoles (0.14 gramsactive of 14.0 wt % in cyclohexane), and purified cyclohexane (195 g).The reactor is then flame sealed off. Diethylether 23 grams (0.31 mole)was added from a break-seal ampoule. Purified butadiene monomer (8.10grams, 150 mmoles) is added from a break-seal ampoule. The reactionmixture is stirred for twenty four hours at room temperature. Theliving, functionalized poly(butadienyl)lithium is terminated withdegassed methanol from the last ampoule.2,6-Di-tert-butyl-4-methylphenol (BHT, 0.01%) is added to the polymersolution as an antioxidant. The resultant protected, functionalizedpolymer is isolated by concentration of the organic solution. Theresultant functionalized polybutadiene polymer is characterized by SEC(polybutadiene standards), and had the following properties: M_(n)=5,200g/mole, M_(w)=5,300 g/mole, M_(w)/M_(n)=1.03. ¹H NMR indicates themicrostructure is 55% 1,4 enchainment, and the presence of the benzylprotecting group on the amine functionality.

EXAMPLE 13 Preparation of Alpha-2° Amine Functionalized Polybutadiene

A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N-benzyl-N-methyl)amino]-1-propyllithium 0.82 mmoles (0.14 gramsactive of 14.0 wt % in cyclohexane), and purified cyclohexane (195 g).The reactor is then flame sealed off. Diethylether 23 grams (0.31 mole)was added from a break-seal ampoule. Purified butadiene monomer (8.10grams, 150 mmoles) is added from a break-seal ampoule. The reactionmixture is stirred for twenty four hours at room temperature. Theresulting reaction mixture is transferred to a 500 mL autoclave andsparged with hydrogen at 45° C. The reactor is pressurized to 700 psigwith hydrogen and a Ni/Al catalyst is added slowly to control theresulting exothermic reaction. Enough catalyst is added to achieve asolution concentration of nickel to 100 ppm. The catalyst is prepared inadvance by reacting 1 molar eq. of nickel(II) 2-ethylhexanote with 2molar eq. of triethylaluminum in cyclohexane). After 2 hr ofhydrogenation, the reaction is allowed to cool to room temperature,depressurized and purged with nitrogen. The resultant functionalizedpolymer is precipitated into a large amount of methanol, filtered andwashed with additional methanol. The resultant hydrogenatedfunctionalized polybutadiene polymer is characterized by ¹H NMRindicating near quantitative hydrogenation (>97%) of the unsaturation inthe backbone and deprotection (>97%) of the benzyl protecting group fromthe amine functionality to afford a terminal secondary amine.

EXAMPLE 14 Preparation of Alpha, Omega-2° Amine FunctionalizedPolybutadiene

A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N-benzyl-N-methyl)amino]-1-propyllithium 0.82 mmoles (0.14 gramsactive of 14.0 wt % in cyclohexane), and purified cyclohexane (195 g).The reactor is then flame sealed off. Diethylether 23 grams (0.31 mole)is added from a break-seal ampoule. Purified butadiene monomer (8.10grams, 150 mmoles) is added from a break-seal ampoule. The reactionmixture is stirred for twenty four hours at room temperature. To theliving polymer is added 3-[(N-benzyl-N-methyl)amino]-1-propylchloride(0.16 g, 0.9 mmoles) and is stirred for an additional 15 h at roomtemperature. The resulting reaction mixture is transferred to a 500 mLautoclave and sparged with hydrogen at 45° C. The reactor is pressurizedto 700 psig with hydrogen and a Ni/Al catalyst is added slowly tocontrol the resulting exothermic reaction. Enough catalyst is added toachieve a solution concentration of nickel to 100 ppm. (The catalyst isprepared in advance by reacting 1 molar eq. of nickel(II)2-ethylhexanote with 2 molar eq. of triethylaluminum in cyclohexane).After 2 hr of hydrogenation, the reaction is allowed to cool to roomtemperature, depressurized and purged with nitrogen. The resultanthydrogenated functionalized polybutadiene polymer is characterized by ¹HNMR which verifies near quantitative hydrogenation (>97%) of theunsaturation in the backbone and deprotection (>97%) of the benzylprotecting groups from the amine functionality to afford saturatedpolybutadiene with alpha, omega secondary amine functionalities.

EXAMPLE 15 Preparation of Protected-Alpha-3° Amine FunctionalizedPolyisoprene

A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N,N-dibenzylamino]-1-propyllithium 0.82 mmoles (0.16 grams active of14.0 wt % in cyclohexane), and purified cyclohexane (195 g). The reactoris then flame sealed off. Diethylether 23 grams (0.31 mole) is addedfrom a break-seal ampoule. Purified isoprene monomer (10.20 grams, 150mmoles) is added from a break-seal ampoule. The reaction mixture isstirred for twenty four hours at room temperature. The living,functionalized poly(isoprenyl)lithium is terminated with degassedmethanol from the last ampoule. 2,6-Di-tert-butyl-4-methylphenol (BHT,0.01%) is added to the polymer solution as an antioxidant. The resultantprotected, functionalized polymer is isolated by concentration of theorganic solution. The resultant functionalized polyisoprene polymer ischaracterized by SEC (polyisoprene standards), and had the followingproperties: M_(n)=5,200 g/mole, M_(w)=5,300 g/mole, M_(w)/M_(n)=1.03. ¹HNMR verifies a microstructure of 55% 1,4 enchainment, and the presenceof the benzyl protecting group on the amine functionality.

EXAMPLE 16 Preparation of Alpha-1° Amine Functionalized Polyisoprene

A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N,N-dibenzylamino]-1-propyllithium 0.82 mmoles (0.16 grams active of14.0 wt % in cyclohexane), and purified cyclohexane (195 g). The reactoris then flame sealed off. Diethylether 23 grams (0.31 mole) was addedfrom a break-seal ampoule. Purified isoprene monomer (10.20 grams, 150mmoles) is added from a break-seal ampoule. The reaction mixture isstirred for twenty four hours at room temperature. The resultingreaction mixture is transferred to a 500 mL autoclave and sparged withhydrogen at 45° C. The reactor is pressurized to 700 psig with hydrogenand a Ni/Al catalyst is added slowly to control the resulting exothermicreaction. Enough catalyst is added to achieve a solution concentrationof nickel to 100 ppm. (The catalyst is prepared in advance by reacting 1molar eq. of nickel(II) 2-ethylhexanote with 2 molar eq. oftriethylaluminum in cyclohexane). After 2 hr of hydrogenation, thereaction is allowed to cool to room temperature, depressurized andpurged with nitrogen. The resultant functionalized polymer isprecipitated into a large amount of methanol, filtered and washed withadditional methanol. The resultant hydrogenated functionalizedpolyisoprene polymer is characterized by ¹H NMR which verifies nearquantitative hydrogenation (>97%) of the unsaturation in the backboneand deprotection (>97%) of the benzyl protecting group from the aminefunctionality to afford a terminal primary amine.

EXAMPLE 17 Preparation of Alpha, Omega-1° Amine FunctionalizedPolyisoprene

A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N,N-dibenzylamino]-1-propyllithium 0.82 mmoles (0.16 grams active of14.0 wt % in cyclohexane), and purified cyclohexane (195 g). The reactoris then flame sealed off. Diethylether 23 grams (0.31 mole) was addedfrom a break-seal ampoule. Purified isoprene monomer (10.20 grams, 150mmoles) is added from a break-seal ampoule. The reaction mixture isstirred for twenty four hours at room temperature. To the living polymeris added 3-[(N,N-dibenzylamino]-1-propylchloride (0.25 g, 0.9 mmoles)and is stirred for an additional 15 h at room temperature. The resultingreaction mixture is transferred to a 500 mL autoclave and sparged withhydrogen at 45° C. The reactor is pressurized to 700 psig with hydrogenand a Ni/Al catalyst is added slowly to control the resulting exothermicreaction. Enough catalyst is added to achieve a solution concentrationof nickel to 100 ppm. (The catalyst is prepared in advance by reacting 1molar eq. of nickel(II) 2-ethylhexanote with 2 molar eq. oftriethylaluminum in cyclohexane). After 2 hr of hydrogenation, thereaction is allowed to cool to room temperature, depressurized andpurged with nitrogen. The resultant hydrogenated functionalizedpolyisoprene polymer is characterized by ¹H NMR which verifies nearquantitative hydrogenation (>97%) of the unsaturation in the backboneand deprotection (>97%) of the benzyl protecting groups from the aminefunctionality to afford saturated polyisoprene with alpha, omega primaryamine functionalities.

EXAMPLE 18 Preparation of Protected-Alpha-3° AmineFunctionalized-Polybutadiene

A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N,N-dibenzylamino]-1-propyllithium 0.82 mmoles (0.16 grams active of14.0 wt % in cyclohexane), and purified cyclohexane (195 g). The reactoris then flame sealed off. Diethylether 23 grams (0.31 mole) was addedfrom a break-seal ampoule. Purified butadiene monomer (8.10 grams, 150mmoles) is added from a break-seal ampoule. The reaction mixture isstirred for twenty four hours at room temperature. The living,functionalized poly(butadienyl)lithium is terminated with degassedmethanol from the last ampoule. 2,6-Di-tert-butyl-4-methylphenol (BHT,0.01%) is added to the polymer solution as an antioxidant. The resultantprotected, functionalized polymer is isolated by concentration of theorganic solution. The resultant functionalized polybutadiene polymer ischaracterized by SEC (polybutadiene standards), and had the followingproperties: M_(n)=5,200 g/mole, M_(w)=5,300 g/mole, M_(w)/M_(n)=1.03. ¹HNMR indicates the microstructure is 55% 1,4 enchainment, and thepresence of the benzyl protecting groups on the amine functionality.

EXAMPLE 19 Preparation of Alpha-1° Amine Functionalized Polybutadiene

A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N,N-dibenzylamino]-1-propyllithium 0.82 mmoles (0.16 grams active of14.0 wt % in cyclohexane), and purified cyclohexane (195 g). The reactoris then flame sealed off. Diethylether 23 grams (0.31 mole) was addedfrom a break-seal ampoule. Purified butadiene monomer (8.10 grams, 150mmoles) is added from a break-seal ampoule. The reaction mixture isstirred for twenty four hours at room temperature. The resultingreaction mixture is transferred to a 500 mL autoclave and sparged withhydrogen at 45° C. The reactor is pressurized to 700 psig with hydrogenand a Ni/Al catalyst is added slowly to control the resulting exothermicreaction. Enough catalyst is added to achieve a solution concentrationof nickel to 100 ppm. (The catalyst is prepared in advance by reacting 1molar eq. of nickel (II) 2-ethylhexanote with 2 molar eq. oftriethylaluminum in cyclohexane). After 2 hr of hydrogenation, thereaction is allowed to cool to room temperature, depressurized andpurged with nitrogen. The resultant functionalized polymer isprecipitated into a large amount of methanol, flittered and washed withadditional methanol. The resultant hydrogenated functionalizedpolybutadiene polymer is characterized by ¹H NMR verifying nearquantitative hydrogenation (>97%) of the unsaturation in the backboneand deprotection (>97%) of the benzyl protecting groups from the aminefunctionality to afford an alpha primary amines.

EXAMPLE 20 Preparation of Alpha, Omega-2° Amine FunctionalizedPolybutadiene

A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N,N-dibenzylamino]-1-propyllithium 0.82 mmoles (0.16 grams active of14.0 wt % in cyclohexane), and purified cyclohexane (195 g). The reactoris then flame sealed off. Diethylether 23 grams (0.31 mole) was addedfrom a break-seal ampoule. Purified butadiene monomer (8.10 grams, 150mmoles) is added from a break-seal ampoule. The reaction mixture isstirred for twenty four hours at room temperature. To the living polymeris added 3-[(N,N-dibenzylamino]-1-propylchloride (0.25 g, 0.9 mmoles)and is stirred for an additional 15 h at room temperature. The resultingreaction mixture is transferred to a 500 mL autoclave and sparged withhydrogen at 45° C. The reactor is pressurized to 700 psig with hydrogenand a Ni/Al catalyst is added slowly to control the resulting exothermicreaction. Enough catalyst is added to achieve a solution concentrationof nickel to 100 ppm. (The catalyst is prepared in advance by reacting 1molar eq. of nickel (II) 2-ethylhexanote with 2 molar eq. oftriethylaluminum in cyclohexane). After 2 hr of hydrogenation, thereaction is allowed to cool to room temperature, depressurized andpurged with nitrogen. The resultant hydrogenated functionalizedpolybutadiene polymer is characterized by ¹H NMR which indicates nearquantitative hydrogenation (>97%) of the unsaturation in the backboneand deprotection (>97%) of the benzyl protecting groups from the aminefunctionality to afford saturated polybutadiene with alpha, omegaprimary amine functionalities.

Many modifications and other embodiments of the invention will come tomind to one skilled in the art to which this invention pertains havingthe benefit of the teachings presented in the foregoing descriptions andthe associated drawings. Therefore, it is to be understood that theinvention is not to be limited to the specific embodiments disclosed andthat modifications and other embodiments are intended to be includedwithin the scope of the appended claims. Although specific terms areemployed herein, they are used in a generic and descriptive sense onlyand not for purposes of limitation.

1. A process for the anionic polymerization of anionically polymerizable compounds comprising the steps of: initiating polymerization of one or more compounds capable of anionic polymerization in a hydrocarbon or mixed hydrocarbon-polar solvent medium with one or more compounds having the formula:

to produce an intermediate living polymer, wherein: M is an alkali metal selected from the group consisting of lithium, sodium and potassium; Z is a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally substituted with aryl or substituted aryl; Q is a saturated or unsaturated hydrocarbyl group derived by the incorporation of one or more unsaturated organic compounds into the M-Z linkage; n is from 0 to 5; R¹ is a protecting group selected from the group consisting of aralkyl, allyl, tertiary alkyl and methyl; and R² is the same as R¹, with the proviso that when R¹ is methyl, R² is not C1-C4 alkyl, or R² is different from R¹ and selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, and substituted heterocycloalkyl, with the proviso that when R² is not the same as R¹, then R² is more stable under conditions used to remove R¹, or each R¹ and R² together with the nitrogen atom to which they are attached form

wherein y is from 1 to 4 and each R¹¹ is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, alkoxy, substituted alkoxy, heteroaryl, substituted heteroaryl, heterocycloalkyl, and substituted heterocycloalkyl; reacting the intermediate living polymer with a terminating, functionalizing, or coupling agent; optionally removing at least one protecting group to liberate at least one functional group; and optionally reacting said at least one liberated functional group with one or more comonomers to form a polymer segment.
 2. The process of claim 1, wherein R¹ is aralkyl, allyl, or tertiary alkyl.
 3. The process of claim 2, wherein R¹ is benzyl or benzyl derivative.
 4. The process of claim 3, wherein the step of removing at least one protecting group comprises hydrogenating said polymer under conditions sufficient to remove said benzyl or benzyl derivative.
 5. The process of claim 2, wherein R¹ is allyl.
 6. The process of claim 5, wherein the step of removing at least one protecting group comprises treating said polymer with a rhodium catalyst under conditions sufficient to remove said allyl group.
 7. The process of claim 2, wherein R¹ is tertiary alkyl.
 8. The process of claim 7, wherein the step of removing at least one protecting group comprises treating said polymer with acid under conditions sufficient to remove said tertiary alkyl group.
 9. The process of claim 1, wherein R¹ is methyl and wherein the step of removing at least one protecting group comprises exposing said polymer to ultraviolet radiation under conditions sufficient to remove said methyl group.
 10. The process of claim 2, wherein R² is the same as R¹.
 11. The process of claim 2, wherein R² is methyl.
 12. The process of claim 1, wherein said compound is 3-[(N-benzyl-N-methyl)amino]-1-propyllithium.
 13. The process of claim 1, wherein said compound is 3-[(N,N-dibenzyl)amino]-propyllithium.
 14. The process of claim 1, wherein said compound is 3-[(N-tert-butyl-N-methyl)amino]-1-propyllithium.
 15. The process of claim 1, wherein said compound is 3-[(N,N-di-tert-butyl)amino]-1-propyllithium.
 16. The process of claim 1, wherein at least one liberated functional group is a nitrogen group and wherein said one or more comonomers is selected from the group consisting of diisocyanates to afford a polyurethane polymer segment, dicarboxylic acids to afford a polyamide condensation polymer segment, epoxy resins to afford an epoxy resin polymer segment, anhydrides to afford a carboxyl group, glycidol to afford an hydroxyl terminated epoxy group, and acrylate functionalized epoxides to afford an olefinic group.
 17. The process of claim 1, further comprising hydrogenating said polymer before or after said optional deprotection step. 